Method of polymerizing nonwrinkling oils to wrinkling oils



mama May 18, 1948 METHOD OI IOLYMEBIZING NONWRIN- KLING OILS TO WRINKLING OILS Gordon M. Williams, Glens Falls, N. E, M nor to New Wrinkle. Ina, Dayton, Ohio, a oorpo-.

ration of Delaware No Application April 9, 1947,

Serial No. 740,479

Claims. (ol. 260-401) This invention relates to drying oils having the property of yielding wrinkle films when compounded with resins and driers to form a varnish and applied to a surface and dried.

This application is a division of my copending application, Serial Number 485,646, filed May 4, 1943, now Patent No. 2,431,357.

More particularly, the present invention relates to means whereby polymerization nuclei may be initially formed whereby to improve or increase the drying rate and wrinkle forming properties of drying oils by treatment according to the present invention.

In the formation of surface wrinkles on a coating composition it is important that there be developed a considerable degree of strain caused by contraction or expansion, or both, between the surface layer and the body of the drying film. While the mechanism of drying of coating films is not clearly understood, it is believed to include polymerization (see Bennett's Driers and Dry.-

ing, page 5, 1941, published by Chemical Publish- 1 ing Company, Brooklyn, New York). Apparently,

this contraction or expansion of the surface layer is a condition established by the initial formation of polymerized nuclei on the surface of the coating film to form a thin skin and the subsequent polymerization of the underlayers. This ference in drying characteristics between tung-- oil (China-wood oil) and other oils such as linseed oil is largely due to the fact that the former by virtue of its high degree of conju ation and symmetry is able to form a closely knit three dimensional polymerized nucleus. Linseed oil and other similar oils, on the other hand, form drawn out-polymerized units which are comparatively loosely knit.

The present invention deals particularly with means whereby the initial formation of polymerizing nuclei may be established in drying oils which are normally nonwrinkling in order to accelerate their drying rate and to improve and fully develop their wrinkle forming characteristics. This is brought about particularly by the introduction in said oils of organometallic comtends to set up the required strain and causes the formation of the wrinkle texture or pattern. It is thus apparent that acceleration of the rate of formation of polymerized units, first on the surface layer and finally throughout the coating film, will aid materially in the speedy formation of the wrinkle texture or pattern which is desired. Furthermore, it is reasonable to assume that the more closely knit the polymerized associations are, the more uniform and pronounced will be the resulting wrinkle patte or texture.

The exact manner in which the molecules of a drying oil orient themselves and interreact is not known. However, there is considerable evidence to indicate that polar bodies are first formed by the introduction of oxygen into the points of unsaturation. These polar molecules are then able to polymerize and form nuclei for further polymerization, and this gradual polymerization of polar molecules leads ultimately to the hardening of the coating film.

Furthermore, it is understood that the difpounds and metallic ions which serve to initiate polymerization and which tend largely to eliminate the necessity for the initial formation of polar bodies by means of oxidation of the oil. For example, linseed oil and soya bean oil are considered to be normally nonwrinkling oils; however, .if these oils are subjected to blowing they are readily transformed into wrinkling oils and the reason for this transformation is believed to be the formation of polar bodies due to the partial oxidation or the introduction of oxygen in the oil molecules.

It should be noted carefully that the selection of the metallic ion, as well as the corresponding organo radical is ofconsiderable importance and will lead to great variations in the results to be attained. It is reasonable to expect that most of the metals will react under the proper conditions. In some cases it may be necessary to use a catalyst and possibly a preliminary addition reaction in order to accomplish the correct attachment of the metallic ion to the oleflnic bond.

It is important to note here the difierence between the construction of an oil molecule treated in this manner and the ordinary drier composition generally used in the art to accelerate drying of oils. In. this case the metallic ions are attached to one or more carbons at their initial points of unsaturation either by means of organometallic compound or other chemical reactions which will serve to orient the. metallic ion to this position,- while in ordinary driers themetallie ion is reacted. with the acid group to form a C-O-M 3 composition. The resulting diiierence in the polymerization. is quite marked since the C-M linkage allows a much closer network of interreaoting molecules than that experience by any polymerization caused by driers of the general type now employed in the art.

or principal importance in the selection an organo group is the formation of an organometallic compound which will unite readily with the oil to allow the initial polymerization. For the most part aliphatic groupings appear to be most satisfactory although in some cases aromatic and alicyclic radicals yield more desirable results.

Organometallic compounds of the type employed according to thepresent invention are or the general formula RM where the R represents an aliphatic, aromatic or alicyclic radical which may or may not contain unsaturated linkages. The M may represent any one of a number of metallic ions which will form a suitable nucleus for polymerization.

By way of illustration and without thereby intending to limit the present invention, there is given below a diagrammatic presentation of the manner in which a small amount or these compounds can initiate polymerization of the oil molecule. The oleic acid radical and a simple organometallic compound are used.

glyceride made of acid radicals containing more than one unsaturated bond is treated with an 'organometallic compound.

As has been'mentioned hereinbefore, it may be desirable in some cases to add the metallic ion to the olefin linkage by means other than through the use of the organometailic unit. The alkali metals, for instance, will add directly into the double bond and the resulting polymerization is similar to that pictured above.

The fundamental principles of the present invention are applicable to the treatment of other esters of drying oils besides the triglyceride formation. Typical of these are thoseobtained by the reaction of-unsaturated fatty acids with monohydric alcohols and other polyhydric alcohols than trihydric. These substances possess potential drying properties which may be developed under proper conditions and which, with the aid of the polymerizing nucleus which results from the practice of the present invention will harden and produce suitable films.

Further. by way of illustration. and without thereby intending to limit the present invention, the following examples are given:

Example I proximately 4 hours. The heat is then increased to approximately 50 C. for the removal of the ether and then to 200 C. at which temperature it is held for a period of about 4 hours until a rather viscous oil results. The nitrogen supply is shut oi! approximately 1 hour prior to the completion or the cook.

The resulting product is a viscous oil possessing a highly increased drying rate and wrinkle forming properties which when compounded with resin and driers as is customary in the art will produce a coating composition which will yield a well geflirlimegd uniform wrinkle film on application and Example I I 50 grams of an esterifled mixture of linseed oil fatty acids and ethylene glycol are placed in a container such as described in Example I. 0.2 gram of C0(CH2-CH=CH2)2 in 20 grams of diethyl ether are then added to the container. Nitrogen is introduced to provide an inert blanket over the mixture and the stirrerls started. The contents are allowed to react for approximately 2 hours at room temperature and the temperature is then increased to approximately 50 C. for the removal of the ether and then to approximately 250 C. The mixture is maintained at this temperature for about 2 hours and 50 grams of the original ester is then added. At this'point the temperature will rapidly drop, and it is then increased to 200 C. and kept at this level until the oil is quite viscous.

The product resulting from this treatment may be used in the usual manner in compounding wrinkle coating compositions and will produce results not unlike those obtained with the product or Example I.

Example J" 100 grams of soya bean are placed in a container such as described in Example I and 0.15 gram oi Pb(CaH'1)2 added, and the mixture treated in the manner described in Example I. After the removal of the ether, however, the temperature is increased to 300 C. and maintained at that level for approximately 8 hours or until the oil reaches the desired degree of viscosity. The inert blanket of nitrogen is maintained throughout this treatment.

The product resulting from this treatment may be used in the same manner and will exhibit the same properties as the products resulting from the treatment of Examples I and II.

It will be understood that the'foregoing examples are illustrative of the application of the method of the present invention, and that it is not intended to have the present invention limited to or circumscribed b the particular details of procedure, materials, or apparatus thereinset forth or described in view of the fact that the present invention is susceptible to modifications depending on individual preference and conditions without departing from the spirit of this disclosure and the scope or the appended claims.

I claim:

1. The method untreated normally non-wrinkling oil which consists in heating said oil in an inert ambient atmosphere at a maximum temperature of 300 C. with lead dipropyl until the desired viscosity has been obtained.

2. The method of making a wrinkling oil from untreated normally non-wrinkling oil which consists in heating said oil in an inert ambient atmosphere at a maximum temperature of 300 C. with lead dipropy-l for approximately 8 hours.

3. The method of making a wrinkling oil from soya bean oil which consists in heating said 011 in an inert ambient atmosphere at a maximum or making a wrinkling oil from temperature of. 300 C. with lead dipropyl for approximately 8 hours.

4. The method of making a wrinkling oil from untreated normally non-wrinkling oil which consists in adding a solution of substantially 0.15 gram lead dipropyl in substantially 20 grams of diethyl ether to 100 grams of said oil and allowing the mixture to remain at room temperature for approximately 4 hours while maintaining an inert ambient atmosphere; thereafter removing the ether by heating to approximately C.; and thenheating to about 300 C. for approximately 8 hours in an inert atmosphere.

5. The method of making a wrinking oil from soya bean oil which consists in adding a solution of substantially 0.15 gram lead dipropyl in substantially 20 grams of diethyl ether to grams of said oil and allowing the mixture to remain at room temperature for approximately 4 hours while maintaining an inert ambient atmosphere; thereafter removing the ether by heating to approximately 50 C.; and then heating to about 300 C. for approximately 8 hours in an inert atmosphere.

GORDON M. WILLIAMS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,891,203 Ambros Dec. 13, 1932 2,024,103 Krurnbhaar Dec. 10, 1935 2,294,703 Waldie Sept, 1, 1942 2,298,270 Auer Oct. 13, 1942 2,298,271 Auer Oct. 13, 1942 2,298,915 Auer Oct. 13, 1942 2,308,595 Drummond Jan. 19, 1943 

